Synthesis and Hydrophilicity Analysis of bis(propane-1,2-diol) Terminated Polydimethylsiloxanes (PDMSs).

Among silicone oligomers, polydimethylsiloxane (PDMS) is widely used industrially and has the advantage of improving the properties of other compounds, such as flame-retardant polyurethane (PU). However, as there are barriers to the synthesis of PU-grafted siloxane, owing to the polarity difference between isocyanate and PDMS, numerous research efforts are being aimed at improving the hydrophilicity of PDMS. To improve the hydrophilicity and reactivity of hydroxyl PDMS, bis(propane-1,2-diol)-terminated PDMS (G-PDMS-G) with four hydroxy (-OH) groups was synthesized through ring-opening addition to replace both ends of linear α,ω-hydroxyl PDMS (HO-PDMS-OH) with glycidol, resulting in hydrophilic PDMS rather than dihydroxy PDMS. In all cases of G-PDMS-G, the contact angle and viscosity both decreased by more than 20%, confirming the improved hydrophilicity. In particular, G-PDMS-G-3, which has the largest molecular weight, demonstrated the greatest decrease in viscosity and contact angle (33%).

Ultrasensitive FRET-based DNA sensor using PNA/DNA hybridization.

In the diagnosis of genetic diseases, rapid and highly sensitive DNA detection is crucial. Therefore, many strategies for detecting target DNA have been developed, including electrical, optical, and mechanical methods. Herein, a highly sensitive FRET based sensor was developed by using PNA (Peptide Nucleic Acid) probe and QD, in which red color QDs are hybridized with capture probes, reporter probes and target DNAs by EDC-NHS coupling. The hybridized probe with target DNA gives off fluorescent signal due to the energy transfer from QD to Cy5 dye in the reporter probe. Compared to the conventional DNA sensor using DNA probes, the DNA sensor using PNA probes shows higher FRET factor and efficiency due to the higher reactivity between PNA and target DNA. In addition, to elicit the effect of the distance between the donor and the acceptor, we have investigated two types of the reporter probes having Cy5 dyes attached at the different positions of the reporter probes. Results show that the shorter the distance between QDs and Cy5s, the stronger the signal intensity. Furthermore, based on the fluorescence microscopy images using microcapillary chips, the FRET signal is enhanced to be up to 276% times stronger than the signal obtained using the cuvette by the fluorescence spectrometer. These results suggest that the PNA probe system conjugated with QDs can be used as ultrasensitive DNA nanosensors.

A "turn-on" fluorescent microbead sensor for detecting nitric oxide.

Nitric oxide (NO) is a messenger molecule involved in numerous physical and pathological processes in biological systems. Therefore, the development of a highly sensitive material able to detect NO in vivo is a key step in treating cardiovascular and a number of types of cancer-related diseases, as well as neurological dysfunction. Here we describe the development of a fluorescent probe using microbeads to enhance the fluorescence signal. Microbeads are infused with the fluorophore, dansyl-piperazine (Ds-pip), and quenched when the fluorophore is coordinated with a rhodium (Rh)-complex, ie, Rh2(AcO(-))4(Ds-pip). In contrast, they are able to fluoresce when the transition-metal complex is replaced by NO. To confirm the "on/off" mechanism for detecting NO, we investigated the structural molecular properties using the Fritz Haber Institute ab initio molecular simulations (FHI-AIMS) package. According to the binding energy calculation, NO molecules bind more strongly and rapidly with the Rh-core of the Rh-complex than with Ds-pip. This suggests that NO can bond strongly with the Rh-core and replace Ds-pip, even though Ds-pip is already near the Rh-core. However, the recovery process takes longer than the quenching process because the recovery process needs to overcome the energy barrier for formation of the transition state complex, ie, NO-(AcO(-))4-(Ds-pip). Further, we confirm that the Rh-complex with the Ds-pip structure has too small an energy gap to give off visible light from the highest unoccupied molecular orbital/lowest unoccupied molecular orbital energy level.